Caoutchouc substances and process of making same.



- chemists,

FRITZ HOFMANN, CARL COUTELLE, KURT ELBEBFELD, GERMANY, ASSIGNORS &: 00., 0F ELBERFELD, GERMANY, A

MEISENIBURG, AND xomum DElZBRiTCK, or To rannnnranmxnnvonm. FRIEDR. BAYER conrona'non or ennmanr.

CAOUTCiHO-UG SUBSTANCES AND PROCESS OF MAKING SAME.

No Drawing.

Specification of Letters Patent. Application tiled July 10, 1912. Serial No. 708,608.

Patented Dec. 30, 1913.

To all whom it may concern Be it known that we, FRITZ Hor'MANN, GARL COUTELLE, KURT MEISENBURG, and KONRAD' DELBm'icK, doctors of philosophy,

citizens of the German Empire, residing at Elberfeld, Germany, have invented new and useful Improvements in new Caoutchouc Substances and Processes of Making Same, of which the following is a specification.

We have found that the hydrocarbons of the series CH1 (in t. 3H:

in which however at least one atom of H is substituted by an alkyl group containing more than one atom of carbon, such as ethyl, propyl, butyl, etc., and in which the other H atoms may or may not be substituted, for example:

on, CH2 on:

-C Hy i-Calla g-C4Hg a -cs, 0-0 s,

rim (hag IE2 acid anhydrid, butyric acid, creosote, or p which act as diluents, or in the presence of both such promoting and such diluting agents.

In order to illustrate the new process more -ish fully the following examples are given, the parts being by weight:

Example A: Beta-ethylbutadiene is heated in an autoclave for four weeks to from 90100 C. Unchanged hydrocarbon is removed and the residue is heated for some time in vacuo on the water bath the temperature of which is finally brought to boiling. A liquid distils over, while the new product remains behind.

Example heated for about 2 or 3 months to 7080 C. or until a test sample after distillation leaves a residue behind which is insoluble in alcohol and soluble in coaltar benzene. The resulting mass is then introduced into alcohol while stirring. The polymerization product is thus obtained in the form of an elastic substance. By heating the product in vacuo impurities and unreacted upon hydrocarbon are driven off and the desired caoutchouc like substance remains behind.

The new caoutc-houc substances are whitsubstances soluble in benzene and insoluble in alcohol. They are normally free from protein substances which are always contained in the natural. caoutchouc. They form ozonids, nitrosites and brom addition products. The ozonids correspond generally to the caoutchouc substances from which derived and indirectly to the hydrocarbons from which the caoutchouc substances are formed. They are in the vulcanized form whitish to grayish substances which are not adhesive.

Our method of polymerization may also be applied to mixtures of the above defined substitution derivatives of ervthrene and other hydrocarbons of the erythrene series B: Beta isobutylbutadiene' is and similar groups in various proportions and the thus formed mixtures of new caoutcho'uc substances may be employed in the arts.

Our new caoutchouc substances described herein may be vulcanized and such vulcanized caoutchouc substances may be used in the same manner as vulcanized natural caoutchouc. We can also use a mlxture of our new caoutchou with those described in Nos. 578607, 5 this mixture new caoutch l caoutchouc an mixture to vulcanization.

We claim:

1. The process like substance w a substituted erythrene hydrocarbon t least one substiaining more than one atom til a caoutchouc-like substance luble in alcohol but tions Ser. subj ect may with natura ing which tuting group 'of carbon un is formed which is inso soluble in coalt 2. The process of pr like substance ing a substitu which hydrocar in the beta positi one atom of carbon substance is alcohol but so 3. The process 0 like substance which 0 ing an a carbon which hydroca substituting group co one atom of carbon un' substance is alcohol but solu ing beta-ethy like substance is in alcohol but so 7. The process like substance w ing by heating a sub drocarbon which hydroca one substituting group con one atom of carbon.

8. The process like substance which comp ing by heating a substitute drocarbon w tuting more t of producing a caoutchouchich comprlses polymerizar benzene.

a caoutchoucwhich comprises polymerizted erythrene hydrocarbon bon has a substituting group on containing more th until a caoutchouc-like ch is insoluble in luble in coaltar benzene.

ft producing a oinprises polymerizd erythrene hydrorbon has at least one ntaining more than til a caoutchouc-like ch is insoluble in ble in coaltar benzene.

producing a which comprises substituted erythren hydrocarbon the beta-posi e atom of c formed whi caoutchouc formed whi caoutchouc polymerize hydroubstituttion containing arbon until formed which uble in coaltar l. The process of like substance ing an alkyl carbon which ing group in more than on caoutchouc-li is insoluble in al benzene.

5. The process like substance w ing an ethyl subs carbon until a caoutcl formed which is inso soluble incoaltar benzene.

6. The process of produ like substance which compr l-erythrene unti formed whi luble in coaltar benzene.

of producing a caoutcho-uchich comprises stituted ery cohol but sol of producing a caoutchouc hich comprises polymeriztituted erythrene hydro ouc-like substance is luble in alcohol but cing a caoutchouc ises polymerizl a caoutchoucch is insoluble polymerizthrene hyrbon has at least taining more than ng a caoutchoucrises polymerizd erythrene hyn has a substihich hydrocarbo ntaining group in the beta position co han one atom of carbon.

ke substance which COIIiPIlSBS olymerizc substances for example 9. The process of producing a caoutchouc our other applicali 78608, 58817 3 and ing by heating an alkyl-substitute erythrene to vulcanization, or we hydrocarbon which hydrocarbon has, at least ouc substances one substituting group containing more d subject this i than one atom of carbon.

10. The process of producing a caoutchouc like substance which comprises polymerizing by heating an alkyl substituted erythrene hydrocarbon which hydrocarbon has a substituting group in the beta-position containing more than one atom of carbon;

11. The process of producing a caoutchouc like substance which comprises polymerizing by heating an ethyl substituted erythrene hydrocarbon.

12. The process of producing a caoutchouc like substance which comprises polymerizing by heating beta-ethyl-erythrene.

13. The process of producing a caoutchouclike substance which comprises. polymerizing a ,substituted erythrene hydrocarbon which hydrocarbon has at least one substituting group containing more than one atom of carbon in the presence of a reagent promoting the olymerization until a caoutchouc-like su stance is formed which is insoluble in alcohol but soluble in coaltar benzene.

like substance which comprises polymerizing a substituted erythrene hydrocarbon which hydrocarbon has a substituting group in the beta position containing more than one atom of carbon in the presence of a reagent promoting the polymerization until a cacutchouc-like substance is formed which is inso-luble in alcohol but soluble in coaltar benzene.

15. The process of producing a caoutchouc like substance which comprises polymeriz: ing an alkyl substituted erythrene hydrocarbon which hydrocarbon has at least one substituting group containing more than one atom of carbon in the presence of a reagent promoting the polymerization until a caoutchouc-like substance is formed which is insoluble in alcohol but soluble in coaltar benzene.

16. The process of producing a caoutchouc like substance which comprises polymerizing an alkyl substituted erythrene hydrocarbon which hydrocarbon has a substituting group in the beta-position containing more than one-atom of carbon in the presence of a reagent promoting the polymerization until a caoutchouc-like substance is formed which is insoluble in alcohol but soluble in coaltar benzene.

17. The process of producing a caoutchouc like substance which comprises polymerizing an ethyl substituted erythrene hydrocarbon in the presence of a reagent promoting the polymerization until a caoutchouclike substance which comprises polymerizbenzene.

ing a substituted erythrene hydrocarbon which hydrocarbon has at least one substituting group containin more than one atom of carbon by heating t e hydrocarbon until a test sam le after suitable distillationleaves a resi us behind which is insoluble in alcohol and soluble in coaltar benzene.

20. The process of producing a caoutchouclike substance which comprises polymerizing a substituted erythrene hydrocarbon which hydrocarbon has a substituting group in the beta position containing more than one atom of carbon by heating the hydrocarbon until a test sample after suitable distillation leaves a residue behind which is insoluble in alcohol and soluble in coaltar benzene.

21. The process of producing a caoutchouc like substance which comprises polymerizing an alkyl substituted erythrene hydrocarbon which hydrocarbon has at least one substituting group containing more than one atom of carbon by heating the hydrocarbon until a test sample after suitable distillation leaves a residue behind which is insoluble in alcohol and soluble in co-altar benzene.

22. The process of producing a caoutchouc like substance which comprises polymerizing a substituted erythrene hydrocarbon which hydrocarbon has a substituting group in the beta-position containing more than one atom of carbon by heating the hydrocarbon until a test sample after suitable distillation leaves a residue behind which is insoluble in alcohol and soluble in coaltar benzene.

23. The process of producing a caoutchouc like substance which comprises polymerizing an ethyl substituted erythrene hydrocarbon by heating the hydrocarbon until a test sample after suitable distillation leaves a residue behind which is insoluble in alcohol and soluble in coal-tar benzene.

24. The process of producing a caoutchouc like substance which comprises polymerizing beta-ethylerythrene by heating the hy-. drocarbon until a test sample after suitable distillation leaves a residue behind which is insoluble in alcohol and soluble in coaltar 25. As a new product a caoutchouc-like substance comprising the caoutchouc-like polymerization product of a substituted erythrene hydrocarbon which hydrocarbon has a substituting group containing more than one-atom of carbon, said product being in-. soluble in alcohol but soluble in coaltar benzene, forming ozonids, nitrosites and brom addition-products, the ozonids corresponding indirectly to the erythrene hydrocarbons from which obtained, and said product be ing capable of vulcanization and being in the vulcanized form a whitish to grayish non-adhesive substance.

26. As a new product a caoutchouc-like substance comprising the caoutchouc-like polymerization product of a substituted erythrene hydrocarbon which hydrocarbon has a substituting group in the beta-positlon containing more than'one atom of carnitrosites and brom addition products the ozonids corresponding indirectly to the erythrene hydrocarbons from which obtained, and said product being capable of vulcanization and being in the vulcanized form a whitish to grayish non-adhesive substance.

27. As a new product a caoutchouc like substance comprising the caoutchouc like polymerization product of an alkyl substituted erythrene hydrocarbon which hydrocarbon has a substituting group containing more than one atom of carbon, said product being insoluble in alcohol but soluble in coaltar benzene, forming ozonids, nitrosites and brom addition products, the ozonids corresponding indirectly to the erythrene hydrocarbons from which obtained, and said product being capable of vulcanization and being in the vulcanized form a whitish to grayish non-adhesive substance.

28. As anew product a caoutchouc. like substance comprising the caoutchouc like polymerization product of an alkyl substituted erythrene hydrocarbon which hydrocarbon has a substituting group in the betaposition containing more than one atom of carbon, said product being insoluble in alcohol but soluble in coaltar benzene, forming ozonids, nitrosites and brom addition products,'the ozonids corresponding indirectly to the erythrene hydrocarbons from, which obtained, and said product being capable of vulcanization and being in the vulcanized form. a whitish to grayish non-adhesive substance. v

29. As a new product a caoutchouc like substance comprising an ethyl substituted erythrene caoutchouc, said product being insoluble in alcohol but soluble in coaltar benzene, forming ozonids, nitrosites and brom addition products, the ozonids correspond- 'bon, said product being, insoluble in alcohol but soluble in coaltar benzene, forming ozonids,

ing indirectly to the erythrene hydrocarbons from which obtained, and said product being capable of the vulcanized non-adhesive substance. a

30. As a new Product a caoutchouc like substance compnsing vulcanization and being in vulcanized form is a nod-adhesive whitish form a whitish to grayish to rayish substance.

n testimony whereof we have hereunto 15 set our hands in the presence ofitwo subbeta-ethylerythrene i i witnesses.

caoutchouc. RITZ HOFMANN. [1,. s.] 31. As a new product a caoutchouc like CARL COUTELLE- l 'l substance comprising beta-ethylerythrene KURT MEISENBURG- [L -1 caoutchouc obtained by polymerization of KONRAD DELBRUCK. [n s.]

beta-ethylerythrene which is characterized Witnesses: by being a whitish substance insoluble in HELEN -NUFER, in coaltar benzene and in the ALBER'r NUFER.

alcohol soluble 

